Alkyl-capped alkoxylated esters and compositions comprising same

ABSTRACT

Process of making alkyl-capped alkoxylated esters. More specifically, a process of making alkyl-capped alkoxylated esters that are comprised substantially of triethylene alkoxy ester and substantially free from ethylene glycol monoalkoxy monoester and diethylene glycol monoalkoxy monoester.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a divisional application of U.S. Ser. No.10/990,790, filed Nov. 17, 2004; and U.S. Ser. No. 10/319,935, filedDec. 16, 2002; which claims priority under 37 U.S.C. § 119(e) to U.S.Provisional Application Ser. No. 60/342,724, filed Dec. 20, 2001.

FIELD OF THE INVENTION

The present invention relates to alkyl-capped alkoxylated esters and aprocess of making the same. The compounds of the present inventioncomprised substantially of an alkyl-capped alkoxylated ester havingformula (I).

wherein x being equal to or greater than 3; with the alkyl-cappedalkoxylated esters being substantially free from ethylene glycolmonoalkoxy monoester having the formula (I), wherein x is equal to 1 anddiethylene glycol monoalkoxy monoester having the formula (I), wherein xis equal to 2, to provide a meaningful alternative to conventionalethoxylates, some of which have been associated with higher toxicity andhigher sudsing. When incorporated into a cleaning or detergentcomposition in accordance with the present invention, the claimedalkyl-capped alkoxylated esters exhibit enhanced cleaning performanceand lower toxicity, particularly in comparison to conventionalethoxylates.

BACKGROUND OF THE INVENTION

There exists a plethora of surfactants in the detergency art.Surfactants, which are comprised of both a hydrophilic and a hydrophobicsegment, serve the integral purpose of reducing the surface tension ofthe substrate to which they are applied. Surfactants are particularlyuseful for purposes of wetting, emulsifying, dispersing, foaming,scouring and/or lubricity. Indeed, alcohol ethoxylates (AEs) are commonsurfactants that are employed often for their detergency andemulsification properties.

With the promulgation of recent regulations and initiatives directed atthe reduction of nonylphenol ethoxylates (NPEs), some of which have beenassociated with biodegradation and toxicity issues, other ethoxylateshave become primary alternatives to those skilled in the art.Nevertheless, a few conventional ethoxylated surfactants, too, have beenlinked to adverse affects on the environment. In particular, certainethoxylates characterized by high levels of ethylene glycol monoalkoxymono ester, diethylene glycol monoalkoxy monoester, ethylene glycolalkyl ether, R₁O(CH₂CH₂O)_(n)H, wherein n is equal to 1 and diethyleneglycol alkyl ether, R₁O(CH₂CH₂O)_(n)H, wherein n is equal to 2, havebeen identified.

It is predicted that the use of these ethoxylates will substantiallydecline and will likely result in a deficiency of meaningfulalternatives to conventional surfactants, and particularly the widelyemployed nonylphenol ethoxylates. Thus, there exists a substantial needin the surfactant and detergency arts to identify and deploy meaningfuland environmentally friendly alternatives to conventional ethoxylates,and specifically alcohol ethoxylates, methyl ester ethoxylates, andnonylphenol ethoxylates. Any meaningful enhancement upon saidconventional ethoxylates should deliver the benefits of high performanceand the reduction of negative attributes. Furthermore, any meaningfulimprovement upon conventional ethoxylates should likely convey thebenefit of enhanced biodegradation.

The alkyl-capped alkoxylated esters of the present invention address theproblems associated with conventional ethoxylates, and specificallyalcohol ethoxylates, methyl ester ethoxylates and nonylphenolethoxylates, as will become apparent from the following disclosure.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a mixing apparatus utilized for measuring suds volume.

FIG. 2 is the ethoxylate distribution of the ACAEs of the presentinvention.

SUMMARY OF THE INVENTION

The present invention addresses problems associated with conventionalethoxylates, and specifically alcohol ethoxylates, methyl esterethoxylates and nonylphenol ethoxylates. Indeed, the alkyl-cappedalkoxylated ester compounds (hereinafter “ACAEs”) of the presentinvention are characterized by high performance and reduction ofnegative attributes, particularly in comparison to conventionalethoxylates. Moreover, the compounds of the present invention experienceenhanced biodegradation. An embodiment of the present invention is analkyl-capped alkoxylated ester having the formula (I):

wherein R₁ is a C₁ to C₄ hydrocarbon, linear or branched, and mixturesthereof, R₂ is C₇ to C₂₂ hydrocarbon, linear or branched, and mixturesthereof; and x is equal to or greater than 3; such that the alkyl-cappedalkoxylated ester is substantially free of ethylene glycol monoalkoxymonoester having formula (I) wherein x is equal to 1 and diethyleneglycol monoalkoxy monoester having formula (I) wherein x is equal to 2,and is substantially free of ethylene glycol alkyl ether (R₁O(CH₂CH₂O)Hunit) and diethylene glycol alkyl ether (R₁O(CH₂CH₂O)₂H unit).

Another embodiment of the present invention is the process of preparingan alkyl-capped alkoxylated ester, having the formula (I).

wherein R₁ is a C₁ to C₄ hydrocarbon, linear or branched, and mixturesthereof, R₂ is C₇ to C₂₂ hydrocarbon, linear or branched, and mixturesthereof; and x is equal to or greater than 3. The claimed processcomprises the steps of ethoxylating a compound having the structuralformula: R₁O(CH₂CH₂O)_(n)H wherein R₁ is defined as above and the indexof n is greater than or equal to 3; wherein said compound,R₁O(CH₂CH₂O)_(n)H, is comprised substantially of ethylene glycol alkylethers, R₁O(CH₂CH₂O)_(n)H, wherein n is equal to or greater than 3, andis substantially free of ethylene glycol alkyl ether, R₁O(CH₂CH₂O)Hunit, wherein n of the ethylene glycol alkyl ethers formula is equal to1; and diethylene glycol alkyl ether, R₁O(CH₂CH₂O)₂H unit, wherein n ofthe ethylene glycol alkyl ethers formula is equal to 2; by reacting saidcompound with an ethoxylating agent having the formula (II):

and conducting the ethoxylation step in the presence of a base; definedherein below, reacting the product of said ethoxylation step withformula (III):

wherein R₂ is as defined above in formula (I) and R₃ is a C₁ to C₄hydrocarbon, linear or branched, and mixtures thereof; wherein saidreaction in the presence of a base catalyst, defined herein below;heating to a temperature of from about 60° C. to about 200° C.; andoptionally, at a pressure from about 20 kPa to about 0.013 kPa (200 mmHg to 0.1 mm Hg) for 0.1 to 10 hours.An embodiment of the present invention comprises another process forpreparing the ACAEs, having the formula (I). The process comprises thesteps of: stripping substantially a conventional polyethylene glycolalkyl ethers of ethylene glycol alkyl ether (R₁O(CH₂CH₂O)H unit) anddiethylene glycol alkyl ether (R₁O(CH₂CH₂O)₂H unit); reacting thestripped product with a compound having the formula (III) in thepresence of a base catalyst, defined herein below, heating to atemperature of from about 60° C. to about 200° C., optionally, at apressure ranging from about 20 kPa and about 0.013 kPa (200 mm Hg to 0.1mm Hg) for 0.1 to 10 hours, and optionally, recycling said ethyleneglycol alkyl ether (R₁O(CH₂CH₂O)H unit) and diethylene glycol alkylether (R₁O(CH₂CH₂O)₂H unit) from the first step of said reaction.

Another embodiment of the present invention incorporates the ACAEs intocleaning compositions.

These and other objects, features, and advantages will become apparentto those of ordinary skill in the art from a reading of the followingdetailed description and the appended claims. All percentages, ratiosand proportions herein are by weight of a cleaning composition unlessotherwise specified. All temperatures are in degrees Celsius (° C.)unless otherwise specified. All documents cited are in relevant part,incorporated herein by reference.

DETAILED DESCRIPTION OF THE INVENTION

The alkyl-capped alkoxylated esters of the present invention aresubstantially free of conventional ethylene glycol monoalkoxy monoesterhaving the formula (I).

wherein x is equal to 1, herein after referred to as “R₁E₁” constituentsand diethylene glycol monoalkoxy monoester having the formula (I)wherein x is equal to 2, herein after referred to as “R₁E₂”constituents. Additionally, the alkyl-capped alkoxylated esters of thepresent invention are substantially free of ethylene glycol alkyl ether(R₁O(CH₂CH₂O)H unit) and diethylene glycol alkyl ether (R₁O(CH₂CH₂O)₂Hunit). “Substantially free” is defined herein to mean that R₁E₁ and R₁E₂constituents and the R₁O(CH₂CH₂O)H unit and R₁O(CH₂CH₂O)₂H unit compriseless than 5% by weight of the alkyl-capped alkoxylated esters,preferably from about 1% to 0% by weight of the alkyl-capped alkoxylatedesters. Conversely, “substantially free” means that the resultingalkyl-capped alkoxylated esters comprises from about 95% to about 100%,preferably about 99% to about 100% of a constituent of formula (I)wherein x is equal to or greater than 3.

As used herein “conventional ethoxylates” include but are not limited toalcohol ethoxylates, methyl ester ethoxylates, and nonylphenolethoxylates. As used herein “cleaning compositions” include, but are notlimited to household cleaning compositions such as hard surface cleaners(i.e., floor cleaners, glass cleaners) granular laundry detergents,liquid laundry detergents, toilet cleaners, car cleaners, carpetcleaners, appliance cleaners, wall cleaners and non-aqueous basedcleaning systems, including many of the newer systems which are based onsilicones, ethers or carbon dioxide, inter alia.

Alkyl-Capped Alkoxylated Ester Compounds (ACAE)

The alkyl-capped alkoxylated ester compounds (“ACAE”) of the presentembodiment is illustrated by formula (I):

wherein R₁ is a C₁ to C₄ hydrocarbon, linear or branched, and mixturesthereof, R₂ is C₇ to C₂₂ hydrocarbon, linear or branched and mixturesthereof and the index of x is equal to or greater than 3. The ACAEs ofthe present invention provide a meaningful and viable alternative toconventional ethoxylates, such as R₁E₁ and R₁E₂, alcohol ethoxylates,methyl ester ethoxylates and nonylphenol ethoxylates.Process

In accordance with the present invention, a process for preparing theACAEs of the claimed invention, is disclosed. Thus, the presentembodiment relates to a preferred process of preparing the ACAEsdiscussed above having the formula (I).

wherein R₁ is a C₁ to C₄ hydrocarbon, linear or branched, and mixturesthereof, R₂ is C₇ to C₂₂ hydrocarbon, linear or branched and mixturesthereof and the index of x is equal to or greater than 3. The claimedprocess comprises the steps of ethoxylating a starting material havingformula R₁O(CH₂CH₂O)_(n)H; wherein R₁ is as defined above in formula (I)and the index of n is greater than or equal to 3; wherein said startingmaterial is substantially free of ethylene glycol alkyl ether(R₁O(CH₂CH₂O)H unit) and diethylene glycol alkyl ether (R₁O(CH₂CH₂O)₂Hunit), and reacting said starting material with an ethoxylating agenthaving the formula (II):

conducting the ethoxylation step in the presence of a base, discussedbelow; to form a product of said ethoxylation. Next, reacting theproduct of said ethoxylation with a compound having the formula (III):

wherein R₂ is defined as above for formula (I) and R₃ is a C₁ to C₄linear or branched hydrocarbon or mixtures thereof;conducting said reaction in the presence of a base catalyst, discussedbelow; applying heat to said reaction, ranging in temperature of fromabout 60° C. to about 200° C.; and optionally, conducting said all orpart of said process in a vacuum ranging from about 20 kPa to about0.013 kPa (200 mm Hg to 0.1 mm Hg), preferably about 3.33 kPa to about0.133 kPa (25 mm to 1 mm Hg), for a period of time ranging from 0.1 to10 hours to form the ACAEs of the present invention.

The base used for ethoxylation can be any of the conventional basesknown in the art. Non-limiting examples such as NaOH, Na metal, KOH,Mg(OH)₂, Ca(OH)₂, Rare earth alkoxides, are all of bases which may beused for the ethoxylation. Additionally, acceptable bases include, butare not limited to, conventional and narrow range alkoxylationcatalysts. Although not preferred acidic ethoxylation catalysts such asBF₃ and others reported in the art may be used.

The base catalysts may be the same as the base described above for thethe ethoxylation step or may differ from the base used for theethoxylation step. Indeed, the practitioner of the invention may choosenot to add any additional base catalyst if the base from theethoxylation step is not neutralized, since the base from theethoxylation step should be sufficient in acting additionally as thebase catalyst to carry out the second step of said process to preparethe ACAE's of the present invention.

Thus, in accordance with another preferred embodiment of the presentinvention, an alternative process with which to generate the ACAEs ofthe present invention is disclosed. The ACAEs of the present inventionare illustrated by the following chemical structure in formula (I):

wherein R₁ is a C₁ to C₄ hydrocarbon, linear or branched, and mixturesthereof, R₂ is C₇ to C₂₂ hydrocarbon, linear or branched, and mixturesthereof, and the index of x is greater than or equal to 3. The processof yielding the compound of formula (I) comprises the steps of strippingsubstantially a conventional polyethylene glycol alkyl ether of ethyleneglycol alkyl ether (R₁O(CH₂CH₂O)H unit) and diethylene glycol alkylether (R₁O(CH₂CH₂O)₂H unit), reacting the stripped product with acompound having the formula (III):

wherein R₂ is as defined in formula (I) above and R₃ is C₁ to C₄hydrocarbon, linear or branched, and mixtures thereof; and conductingsaid reaction in the presence of a base, applying heat to said reaction,ranging in temperature of from about 60° C. to about 200° C.,optionally, conducting all or part of said reaction in a vacuum rangingfrom about 20 kPa to about 0.013 kPa (200 mm Hg to 0.1 mm Hg),preferably about 3.33 kPa to about 0.133 kPa (25 mm Hg to 1 mm Hg), fora period of time ranging from 0.1 to 10 hours to form the ACAEs of thepresent invention, and optionally, recovering any R₁O(CH₂CH₂O)H unit andR₁O(CH₂CH₂O)₂H unit from the first step of said reaction;

The recovered R₁O(CH₂CH₂O)H unit and R₁O(CH₂CH₂O)₂H unit from the firststep of said reaction may optionally be used to prepare additionalconventional polyethylene glycol alkyl ether for use in said process,thus making the process more economical.

The stripping of the conventional polyethylene glycol alkyl etherconstitutes a fundamental step in the above-described processembodiment. As used herein “stripping substantially” is defined ashaving the conventional polyethylene glycol alkyl ether, upon beingstripped, possesses from about 95% to about 100%, preferably 99% to100%, of R₁O(CH₂CH₂O)_(n)H, units wherein n is equal to or greater than3. The term “stripping substantially” may also be defined on the basisof the R₁O(CH₂CH₂O)H unit and R₁O(CH₂CH₂O)₂H unit content of thestripped, polyethylene glycol alkyl ether of the present processembodiment. Upon stripping, said polyethylene glycol alkyl etherpossesses from about 5% to about 0%, preferably 1% to 0%, ofR₁O(CH₂CH₂O)H unit and R₁O(CH₂CH₂O)₂H unit. To reiterate, it is believedthat the stripping step of the process of the present embodiment ensuresthat the resultant, ACAEs are substantially free from R₁E₁ and/or R₁E₂constituents as well as any remaining unreacted R₁O(CH₂CH₂O)H and/orR₁O(CH₂CH₂O)₂H units, and is thereby characterized by low toxicity andlow sudsing, particularly in comparison to conventional ethoxylates.

Indeed, said stripping may be achieved a variety of ways. Nonlimitingexamples of preferred laboratory procedures that may be performed tostrip the polyethylene glycol alkyl ethers of the present processinclude: distillation, vacuum distillation, thin film evaporation andcombinations thereof. In a preferred embodiment of the presentinvention, said stripping may be conducted as an initial step of saidprocess. In yet another preferred embodiment of the present invention,said stripping may be conducted as a final step of said process. Toreiterate, the different process embodiments of the present inventionare intended to serve different means with which to yield the ACAEs ofthe present invention. Some who practice the present invention maydiscover that the process of stripping the R₁O(CH₂CH₂O)H unit andR₁O(CH₂CH₂O)₂H unit from commercially available, conventionalpolyethylene glycol alkyl ether, presents an easier and/or lessexpensive means in which to generate the ACAEs of the present invention.Nevertheless, the selection of the appropriate process of the claimedinvention is entirely within the discretion of the practitioner, as bothprocesses are adapted to yield the ACAEs of the present invention.

Another embodiment of the present invention relates to a process ofmaking the ACAEs having the formula (I):

wherein R₁ is a C₁ hydrocarbon (methyl), linear or branched, andmixtures thereof, R₂ is C₇ to C₂₂ hydrocarbon, linear or branched, andmixtures thereof, and the index of x is greater than or equal to 3.The claimed process comprises the steps of ethoxylating a startingmaterial having formula R₁O(CH₂CH₂O)_(n)H; wherein R₁ is a C₁hydrocarbon (methyl) and the index of n is greater than or equal to 3;wherein said starting material is substantially free of ethylene glycolalkyl ether (R₁O(CH₂CH₂O)H unit) and diethylene glycol alkyl ether(R₁O(CH₂CH₂O)₂H unit), and reacting said starting material with anethoxylating agent having the formula (II):

conducting the ethoxylation step in the presence of a base; reacting theproduct of said ethoxylation with a compound having the formula (III):

wherein R₂ is a C₇ to C₂₂ hydrocarbon, linear or branched, and mixturesthereof; and R₃ is a C₁ to C₄ linear or branched hydrocarbon or mixturesthereof; conducting said reaction in the presence of a base catalyst,applying heat to said reaction, ranging in temperature of from about 60°C. to about 200° C.; and optionally, conducting said all or part of saidprocess in a vacuum ranging from about 20 kPa to about 0.013 kPa (200 mmHg to 0.1 mm Hg), preferably about 3.33 kPa to about 0.133 kPa (25 mm to1 mm Hg), for a period of time ranging from 0.1 to 10 hours to form amethyl fatty ester of formula (I).

The resulting methyl fatty ester of formula (I) is then reacted withethylene oxide units via addition polymerization to form the ACAEs ofthe present invention. Preferably, the addition polymerization processutilizes a metal-oxide catalyst process described in U.S. Pat. No.5,817,844 B1, Hama et al.; wherein the metal-oxide catalyst consistsessentially of calcined aluminum magnesium hydroxide whose surface ismodified with a metal hydroxide or a metal alkoxide. Additionally, apreferable additional polymerization process using suitable catalystsare discussed in EP 0 889 872 B1, which utilizes (a) alkali metal and/oralkaline earth metal hydroxides and/or alcoholates and (b) alkyleneglycols as catalysts.

Product of Process

In yet another, preferred aspect of the present invention, the productof the aforementioned process is disclosed and claimed. The productyielded by performing the process of the present embodiment isillustrated by formula (I):

wherein R₁ is a C₁ to C₄ hydrocarbon, linear or branched, and mixturesthereof, R₂ is C₇ to C₂₂ hydrocarbon, linear or branched, and mixturesthereof, and the index of x is greater than or equal to 3; wherein theproduct yielded by performing the process of the present embodiment issubstantially free from R₁E₁, R₁E₂, R₁O(CH₂CH₂O)H, and R₁O(CH₂CH₂O)₂H.Indeed, the ACAEs produced by performing the process of the presentembodiment, provide a meaningful and viable alternative to conventionalethoxylates, and specifically alcohol ethoxylates, methyl esterethoxylates and nonylphenol ethoxylates.

Without wishing to be bound by theory, it is believed that by conductingthe ethoxylation step of the above process with an ethoxylate that iscomprised substantially of an ethylene glycol alkyl ether(R₁O(CH₂CH₂O)_(n)H,) wherein n is equal to or greater than 3, andsubstantially free of ethylene glycol alkyl ether (R₁O(CH₂CH₂O)H) anddiethylene glycol alkyl ether (R₁O(CH₂CH₂O)₂H), the resultant ACAE isalso substantially free from R₁E₁ and R₁E₂ constituents. The product ofthe process of the present embodiment is characterized by low toxicity,particularly in comparison to conventional ethoxylates, and specificallyalcohol ethoxylates, methyl ester ethoxylates and nonylphenolethoxylates. Moreover, the product of the present process comprises theadditional benefit of low sudsing, particularly when compared toconventional ethoxylates. The low sudsing characteristics of the presentcompounds are particularly evident when the compounds are employed in acleaning composition.

Cleaning Compositions

The ACAEs of the present invention yielded by performing the presentprocess are substantially free from R₁E₁ and/or R₁E₂ constituents, andis substantially free of ethylene glycol alkyl ether (R₁O(CH₂CH₂O)Hunit) and diethylene glycol alkyl ether (R₁O(CH₂CH₂O)₂H unit); andthereby characterized by low toxicity and low sudsing, particularly incomparison to conventional ethoxylates, and specifically alcoholethoxylates, methyl ester ethoxylates and nonylphenol ethoxylates. Thelow sudsing characteristics of the ACAEs of the present invention areparticularly evident when the ACAEs are employed in a cleaningcomposition. Thus, in accordance with another embodiment of the presentinvention is a cleaning composition comprising the novel, ACAEs of thepresent invention.

The use of the ACAEs of the present invention in cleaning compositionsprovide a meaningful and environmentally friendly alternative to theemployment of conventional ethoxylates, specifically alcoholethoxylates, methyl ester ethoxylates and nonylphenol ethoxylates, in acleaning composition. The ACAEs of the present invention arecharacterized by several, performance benefits, particularly incomparison to conventional ethoxylates. Namely, the ACAEs of the presentinvention, and thus the cleaning compositions in which they areemployed, experience low sudsing, and thus better overall detergency, incomparison to conventional ethoxylates, and specifically when comparedwith alcohol ethoxylates, methyl ester ethoxylates and nonylphenolethoxylates.

Sudsing

Indeed, the low sudsing characteristics of the present invention areparticularly evident when the ACAEs are employed in a cleaningcomposition. To illustrate the low sudsing benefits of the presentACAEs, a dilute detergent solution is prepared with de-ionized watersuch that the concentration of detergent is approximately 6000 ppm. Thisconcentration is based on a dosage of 78 g of detergent in 13L of water,which is typical for a horizontal axis machine wash process. A 100 mLaliquot of the dilute detergent solution is removed and carefully pouredinto a clean 1000 mL glass graduated cylinder. Just prior to mixing,enough concentrated hardness solution (9600 grains per gallon deionizedwater, 2 parts calcium, 1 part magnesium) is added to each cylinder toattain desired solution hardness and the cylinders are capped. A mixingapparatus, as shown in FIG. 1, rotates 4 cylinders simultaneously at arate of 34 revolutions/minute. At selected time intervals of 2.5minutes, the mixing is stopped and a visual reading of the suds volumeis recorded. After mixing is completed, the cylinders are left uncappedand the suds volume is recorded at selected post-mixing time intervalsof 2.5 minutes. The initial solution volume is subtracted from thesereadings to obtain the volume of suds produced.

Each test is performed in duplicate and an average value is reported.Needless to say, performance of the above procedure illustrates,unequivocally, the enhanced sudsing benefits of the claimed ACAEs of thepresent invention in comparison to conventional ethoxylates, andparticularly alcohol ethoxylates.

FIG. 1 shows the mixing apparatus (10) used to measure the suds volumedescribed above. The mixing apparatus (10) comprises an electrical motor(12), which is a Dayton Shaded Pole Gearmotor, model #3M158B, having 115AC volts; 60 Hz, 2.5 Amps, 1/10 horsepower, 113 ln.lb in torque, and 30F/L RPMs, that can be plugged into a power source. Attached to theunderside of the motor (12) is a counter (14), which when wired to themotor indicates the number of rotations of the motor and the mixingapparatus (10). Affixed to and extending from the motor (10) is acrankshaft (16) that is rotated 360° by the motor (10). The motor (12)is mounted to a motor mount wall (18) being of sufficient thickness andwidth to support the motor (12) and sufficient height to allow themixing apparatus (10) to rotate freely about axis X as shown in FIG. 1.The motor mount wall (18) comprises a motor mount wall opening (19),which the crankshaft (16) extends through and the motor mount wallopening (19) is of sufficient diameter to allow the crankshaft (16) torotate freely about axis X. The crankshaft (16) is attached to andterminates at a piece of a main holding frame (20). The main holdingframe (20) comprises four metal pieces orientated relative to each otherto make a generally rectangular shape having a long axis correspondingto the axis X. One of the pieces of the main holding frame (20)perpendicular to the axis X is attached to the crankshaft (16).

In FIG. 1, the pieces of the main holding frame (20) parallel to theaxis X have four semi-circular shapes (not shown) cut into the mainholding frame (20) that are used to hold four capped 1000 mL glassgraduated cylinders (24). Hingedly attached to one piece of the mainholding frame (20) parallel to the axis X is a face holding frame (22)comprising four metal pieced orientated relative to each other to make agenerally rectangular shape having a long axis corresponding to the axisX and an area equal to that of the main holding frame (20). The faceholding frame (22) is hingedly attached to the main holding frame (20)such that the four capped 1000 mL glass graduated cylinders (24) can beheld firmly into place in the four semi-circular shapes of the mainholding frame (20), and at the same time, the four capped 1000 mL glassgraduated cylinders (24) can be easily removed.

Attached to one of the pieces of the main holding frame (20)perpendicular to the axis X, opposite the piece of the main holdingframe (20) attached to the crankshaft (16) is a rod (26). The rod (26)extends from the main holding frame (20) and passes through a rod mountwall (28) comprising a rod mount wall opening (29). The rod mount wall(28) is of sufficient thickness and width to support the rod (26) andsufficient height to allow the mixing apparatus (10) to rotate freelyabout axis X as shown in FIG. 1. The rod mount wall opening (29) is ofsufficient diameter to allow the rod (26) to rotate freely about axis X.

A heavy duty liquid laundry detergent, as given below in Table 1,designed for use in horizontal axis machines, untilized the methylcapped ACAE, from Example 3 below, resulted in 21% to 35% less sudsduring the mixing, or agitation, phase than did the alcohol ethoxylatetested (see Table 2) in the same heavy duty liquid laundry detergentgiven in Table 1 below. In addition, the foam stability of the methylcapped ACAE was much lower as seen in the post mixing results duringwhich the solution is no longer being agitated. These benefits wereobserved at various levels of water hardness shown in Table 2.

Heavy Duty Liquid Laundry Detergent Surfactant System:

TABLE 1 Wt % of Component detergent linear alkyl benzene sulphonate  15% ACAEs of Example 4 or the AE as indicated in Table 2  8.4% C₈₋₁₀amido propyl dimethylamine surfactant  1.4% builders 11.0% enzymes andenzyme stabilizing agents 3.25% dispersants, chelants and opticalbrighteners 2.39% phase stabilizers 19.42%  perfumes, dyes and otheradjunct ingredients    <1%

TABLE 2 Suds Volume (mL) for SUDS Levels during MIXING POST-MIXING 100mL of HDL Solution 0 min. 2.5 min. 5 min. 7.5 min. 2.5 min. 5 min. 0 gpgLUTENSOL ® 24-7 0 405 555 590 565  305  (C12, 14 alcohol 7-moleethoxylate) C₁₆₁₈-8.5 Methyl 0 320 420 470 365  65 capped ACAE ofExample 4 % Reduction vs. AE   21%   24%   20%  35%  79% 6 gpgLUTENSOL ®24-7 0 280 280 265 75 10 C₁₆₁₈-8.5 Methyl 0 180 200 180 10 10capped ACAE of Example 4 % Reduction vs. AE   36%   29%   32%  87%   0%12 gpg LUTENSOL ® 24-7 0 235 260 265 60 10 C₁₆₁₈-8.5 Methyl 0 160 170190 15 10 capped ACAE of Example 4 % Reduction vs. AE   32%   35%   28% 75%   0%

Moreover, under typical horizontal axis machine wash detergentconcentration and water hardness conditions, the ethyl and butyl cappedACAEs of the present invention also produce fewer suds and providereduced foam stability versus conventional alcohol ethoxylate nonionicsurfactants such as the LUTENSOL® 24-7 nonionic surfactant availablefrom BASF. This has been observed in heavy duty liquid laundry detergentformulations based on linear alkyl benzene sulfonate available fromHuntsman as the core surfactant (see Table 3) as well as in experimentalheavy duty liquid laundry detergents based on long mid-chain branchedalkyl sulfates, discussed below, (see Table 4). From a suds reductionstandpoint, the ethyl capped ACAE is preferred. TABLE 3 Sudsing of Testcompounds in HDL formulated with linear alkyl benzene sulfonate SudsVolume (mL) for MIXING POST-MIXING 100 mL of HDL Wash Solution 0 min.2.5 min. 5 min. 7.5 min. 2.5 min. 5 min. 12 gpg LUTENSOL ® 24-7 0 240255 250 115  15  (C12, 14 alcohol 7-mole ethoxylate) C₁₆₁₈-10.5 Ethyl 0135 135 145 10 0 capped ACAE of the present invention % Reduction vs. AE  44%   47%   42%  91% 100%  C₁₆₁₈-10.5 Butyl 0 190 190 195 15 0 cappedACAE of Example 6 % Reduction vs. AE   21%   25%   22%  87% 100% 

TABLE 4 Sudsing of Test compounds in HDL formulated with alkyl sulfatesSuds Volume (mL) for MIXING POST-MIXING 100 mL of HDL Wash Solution 0min. 2.5 min. 5 min. 7.5 min. 2.5 min. 5 min. 12 gpg LUTENSOL ® 24-7 0225 305 345 340  310  (C_(12, 14) alcohol 7-mole ethoxylate) C₁₆₁₈-10.5Ethyl 0  75  95 100 55 40 capped ACAE of the present invention %Reduction vs. AE   67%   69%   71%  84%   87% C₁₆₁₈-10.5 Butyl 0 120 125135 70 55 capped ACAE of Example 6 % Reduction vs. AE   47%   59%   61% 79%   82%

Even though embodiments of the ACAEs as described above are directed toethoxylated materials. Similar structures of ACAEs could be made usingother alkylene oxide moieties, such as propylene oxide moieties, both incombination with ethylene oxide and/or alone.

Formulations

One preferred aspect of the present invention relates to compositionsthat comprise the ACAEs of the present invention. Formulations of thisaspect can be modified for use at any step in the laundry cycle, forexample, as a pre-soak, as an addition to surfactant comprisingcompositions, as a rinse-added composition. Non-limiting examples ofcompositions that may comprise this aspect include: (a) from about 0.01%to about 99% by weight, of one or more ACAEs according to the presentinvention. Yet another embodiment of this aspect comprises, in additionto a suitable carrier, other adjunct ingredients which can enhance theperformance benefits of the ACAEs or which enhance the delivery of thepresent ACAEs to fabric surface.

The cleaning compositions of the present invention further relate to theaspect of detersive surfactant-comprising compositions, said cleaningcompositions comprising:

-   a) from about 0.01% to about 30% by weight of said composition of    one or more ACAEs according to the present invention. Another    embodiment comprises from about 0.1% to about 10% by weight of said    ACAEs,-   b) from about 1% to 60%, preferably 10% to 35% by weight of said    composition of a surfactant system, said surfactant system    comprising:    -   i) from 0.01% of said composition whereas depending upon which        aspect or embodiment of the present invention, the following        ranges are suitable: from about 0.1% to about 100%; from about        1% to about 80%; from about 1% to about 60%, from about 1% to        about 30% by weight of said surfactant system of one or more        anionic surfactants, said anionic surfactants selected from the        group consisting of linear alkyl benzene sulphonates, modified        alkyl benzene sulphonates; linear alkyl sulfates, mid-chain        branched sulfates, linear alkyleneoxy sulfates, mid-chain        branched alkyleneoxy sulfates; and mixtures thereof;    -   ii) optionally, from 0.01%, whereas depending upon which aspect        or embodiment of the present invention, the following ranges are        suitable: from about 0.1% to about 100%; from about 1% to about        80%; from about 1% to about 60%, from about 1% to about 30% by        weight of said surfactant system of one or more nonionic        surfactants selected from the group consisting of alcohols,        alcohol ethoxylates, polyoxyalkylene alkylamides, and mixtures        thereof; and-   c) the balance carriers and other adjunct ingredients.    Surfactant System

The cleaning compositions of the present invention comprise a surfactantsystem. The surfactant systems of the present invention may comprise anytype of detersive surfactant, non-limiting examples of which include oneor more mid-chain branched alkyl sulfate surfactants, one or moremid-chain branched alkyl alkoxy sulfate surfactants, one or moremid-chain branched aryl sulfonate surfactants, one or more non mid-chainbranched sulphonates, sulphates, cationic surfactants, zwitterionicsurfactants, ampholytic surfactants, and mixtures thereof.

The total amount of surfactant present in the compositions of thepresent invention is from about 0.01% by weight, preferably from about0.1% more preferably from about 1% to about 60%, preferably to about 30%by weight, of said composition.

Nonlimiting examples of surfactants useful herein include:

-   a) C₁₁-C₁₈ alkyl benzene sulfonates (LAS);-   b) C₆-C₁₈ mid-chain branched aryl sulfonates (BLAS);-   c) C₁₀-C₂₀ primary, α or ω-branched, and random alkyl sulfates (AS);-   d) C₁₄-C₂₀ mid-chain branched alkyl sulfates (BAS);-   e) C₁₀-C₁₈ secondary (2,3)alkyl sulfates as described in U.S. Pat.    No. 3,234,258 Morris, issued Feb. 8, 1966; U.S. Pat. No. 5,075,041    Lutz, issued Dec. 24, 1991; U.S. Pat. No. 5,349,101 Lutz et al.,    issued Sep. 20, 1994; and U.S. Pat. No. 5,389,277 Prieto, issued    Feb. 14, 1995;-   f) C₁₀-C₁₈ alkyl alkoxy sulfates (AE_(x)S) wherein preferably x is    from 1-7;-   g) C₁₄-C₂₀ mid-chain branched alkyl alkoxy sulfates (BAE_(x)S),    where x is from 1 to 50;-   h) C₁₀-C₁₈ alkyl alkoxy carboxylates preferably comprising 1-5    ethoxy units;-   i) C₁₂-C₁₈ alkyl ethoxylates, C₆-C₁₂ alkyl phenol alkoxylates    wherein the alkoxylate units are a mixture of ethyleneoxy and    propyleneoxy units, C₁₂-C₁₈ alcohol and C₆-C₁₂ alkyl phenol    condensates with ethylene oxide/propylene oxide block polymers inter    alia PLURONIC® ex BASF which are disclosed in U.S. Pat. No.    3,929,678 Laughlin et al., issued Dec. 30, 1975;-   j) C₁₄-C₂₂ mid-chain branched alkyl alkoxylates, BAE_(x), wherein    preferably x is from 1 to 50;-   k) Alkylpolysaccharides as disclosed in U.S. Pat. No. 4,565,647    Llenado, issued Jan. 26, 1986;-   l) Polyhydroxy fatty acid amides having the formula (IV):    wherein R⁷ of formula (IV) is C₅-C₃₁ alkyl; R⁸ of formula (IV) is    selected from the group consisting of hydrogen, C₁-C₄ alkyl, C₁-C₄    hydroxyalkyl, Q of formula (IV) is a polyhydroxyalkyl moiety having    a linear alkyl chain with at least 3 hydroxyls directly connected to    the chain, or an alkoxylated derivative thereof; preferred alkoxy is    ethoxy or propoxy, and mixtures thereof; preferred Q is derived from    a reducing sugar in a reductive amination reaction, more preferably    Q is a glycityl moiety; 0 is more preferably selected from the group    consisting of —CH₂(CHOH)_(n)CH₂OH, —CH(CH₂OH)(CHOH)_(n-1)CH₂OH,    —CH₂(CHOH)₂(CHOR′)(CHOH)CH₂ OH, and alkoxylated derivatives thereof,    wherein n is an integer from 3 to 5, inclusive, and R′ is hydrogen    or a cyclic or aliphatic monosaccharide, which are described in U.S.    Pat. No. 5,489,393 Connor et al., issued Feb. 6, 1996; and U.S. Pat.    No. 5,45,982 Murch et al., issued Oct. 3, 1995.

A non-limiting example of a nonionic surfactant suitable for use in thepresent invention has the formula (V):

wherein R of formula (V) is C₇-C₂₁ linear alkyl, C₇-C₂₁ branched alkyl,C₇-C₂₁ linear alkenyl, C₇-C₂₁ branched alkenyl, and mixtures thereof.

R¹ of formula (V) is ethylene; R² of formula (V) is C₃-C₄ linear alkyl,C₃-C₄ branched alkyl, and mixtures thereof; preferably R² is1,2-propylene. Nonionic surfactants which comprise a mixture of R¹ andR² units preferably comprise from about 4 to about 12 ethylene units incombination with from about 1 to about 4 1,2-propylene units. The unitsmay be alternating, or grouped together in any combination suitable tothe formulator. Preferably the ratio of R¹ units to R² units is fromabout 4:1 to about 8:1. Preferably R² units are attached to the nitrogenatom followed by the balance of the chain comprising from 4 to 8ethylene units.

R³ of formula (V) is hydrogen, C₁-C₄ linear alkyl, C₃-C₄ branched alkyl,and mixtures thereof; preferably hydrogen or methyl, more preferablyhydrogen.

R⁴ of formula (V) is hydrogen, C₁-C₄ linear alkyl, C₃-C₄ branched alkyl,and mixtures thereof; preferably hydrogen. When the index m of formula(V) is equal to 2 the index n of formula (V) must be equal to 0 and theR⁴ unit is absent and is instead replaced by a —[(R¹O)_(x)(R²O)_(y)R³]unit, wherein R¹, R², and R³ are as defined above in formula (V), and xand y are as defined here in below for formula (V).

The index m of formula (V) is 1 or 2, the index n of formula (V) is 0 or1, provided that when m is equal to 1, n is equal to 1; and when m is 2n is 0; preferably m is equal to 1 and n is equal to 1, resulting in one—[(R¹O)_(x)(R²O)_(y)R³] unit and R⁴ being present on the nitrogen. Theindex x of formula (V) is from 0 to about 50, preferably from about 3 toabout 25, more preferably from about 3 to about 10. The index y offormula (V) is from 0 to about 10, preferably 0, however when the indexy is not equal to 0, y is from 1 to about 4. Preferably all of thealkyleneoxy units are ethyleneoxy units. Those skilled in the art ofethoxylated polyoxyalkylene alkyl amide surface active agents willrecognized that the values for the indices x and y are average valuesand the true values may range over several values depending upon theprocess used to alkoxylate the amides.

The mid-chain branched alkyl sulfate surfactants of the presentinvention have the formula (VI):

the alkyl alkoxy sulfates have the formula (VII):

the alkyl alkoxylates have the formula (VIII):

wherein R, R¹, and R² of formulas (VI)-(VIII) are each independentlyhydrogen, C₁-C₃ alkyl, and mixtures thereof; provided at least one of R,R¹, and R² is not hydrogen; preferably R, R¹, and R² are methyl;preferably one of R, R¹, and R² is methyl and the other units arehydrogen. The total number of carbon atoms in the mid-chain branchedalkyl sulfate and alkyl alkoxy sulfate surfactants is from 14 to 20; theindex w of formulas (VI)-(VIII) is an integer from 0 to 13; x offormulas (VI)-(VIII) is an integer from 0 to 13; y of formulas(VI)-(VIII) is an integer from 0 to 13; z of formulas (VI)-(VIII) is aninteger of at least 1; provided w+x+y+z is from 8 to 14 and the totalnumber of carbon atoms in a surfactant is from 14 to 20; R³ of formulas(VII) and (VIII) is C₁-C₄ linear or branched alkylene, preferablyethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,4-butylene, andmixtures thereof. However, a preferred embodiment of the presentinvention comprises from 1 to 3 units wherein R³ is 1,2-propylene,1,3-propylene, or mixtures thereof followed by the balance of the R³units comprising ethylene units. Another preferred embodiment comprisesR³ units which are randomly ethylene and 1,2-propylene units. Theaverage value of the index m of formulas (VII) and (VIII) is at leastabout 0.01. When the index m has low values, the surfactant systemcomprises mostly alkyl sulfates with a small amount of alkyl alkoxysulfate surfactant. Some tertiary carbon atoms may be present in thealkyl chain, however, this embodiment is not desired.

M of formulas (VI) and (VII) denotes a cation, preferably hydrogen, awater soluble cation, and mixtures thereof. Non-limiting examples ofwater soluble cations include sodium, potassium, lithium, ammonium,alkyl ammonium, and mixtures thereof.

Adjunct Ingredients

The following are non-limiting examples of adjunct ingredients useful inthe cleaning compositions of the present invention, The precise natureof these additional components, and levels of incorporation thereof,will depend on the physical form of the composition and the nature ofthe cleaning operation for which it is to be used. Suitable adjunctmaterials include, but are not limited to, surfactants, builders,chelating agents, dye transfer inhibiting agents, dispersants, enzymes,and enzyme stabilizers, catalytic metal complexes, polymeric dispersingagents, clay soil removal/anti-redeposition agents, optical brighteners,suds suppressors, dyes, perfumes, structure elasticizing agents, fabricsofteners, carriers, hydrotropes, phase stabilizers, processing aidsand/or pigments. Other adjuncts well known in the art are also suitablefor use herein.

Builders

The cleaning compositions of the present invention preferably compriseone or more builders or builder systems. When present, the cleaningcompositions will typically comprise at least about 1% by weight of thecleaning composition of builder, preferably from 5% to about 80% byweight of the cleaning composition of a builder; more preferably fromabout 10% to about 30% by weight of the cleaning composition of abuilder.

Inorganic or P-containing builders include, but are not limited to, thealkali metal, ammonium and alkanolammonium salts of polyphosphates(exemplified by the tripolyphosphates, pyrophosphates, and glassypolymeric meta-phosphates), phosphonates, phytic acid, silicates,carbonates (including bicarbonates and sesquicarbonates), sulphates, andaluminosilicates. Examples of silicate builders are the alkali metalsilicates, examples of which include those having a SiO₂:Na₂O ratio inthe range 1.6:1 to 3.2:1 and layered silicates as described in U.S. Pat.No. 4,664,839 Rieck, issued May 12, 1987 which include NaSKS-6® exHoechst. Others include NaSKS-5®, NaSKS-7®, and NaSKS-11® also exHoechst. Examples of carbonate builders are the alkaline earth andalkali metal carbonates as disclosed in German Patent Application No.2,321,001 published on Nov. 15, 1973. Aluminosilicate builders includethose having the empirical formula: [M_(z)(zAlO₂)_(y)]xH₂O, wherein zand y are integers of at least 6, the molar ratio of z to y is in therange from 1.0 to about 0.5, and x is an integer from about 15 to about264, known as Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. Inone embodiment, the crystalline aluminosilicate ion exchange materialhas the formula: Na₁₂[(AlO₂)₁₂(SiO₂)₁₂]xH₂O, wherein x is from about 20to about 30, especially about 27. This material is known as Zeolite A.Preferably, the aluminosilicate has a particle size of about 0.1-10microns in diameter.

Included among the polycarboxylate builders are those disclosed in U.S.Pat. No. 3,128,287 Berg, issued Apr. 7, 1964, and U.S. Pat. No.3,635,830 Lamberti et al., issued Jan. 18, 1972; U.S. Pat. No. 4,663,071Bush et al., issued May 5, 1987; U.S. Pat. No. 3,923,679 Rapko, issuedDec. 2, 1975; U.S. Pat. No. 4,158,635 Crutchfield et al., issued Jun.19, 1979; U.S. Pat. No. 4,120,874 Crutchfield et al., issued Oct. 17,1978; and U.S. Pat. No. 4,102,903 Crutchfield et al., issued Jul. 25,1978. Other useful detergency builders include the etherhydroxypolycarboxylates, copolymers of maleic anhydride with ethylene orvinyl methyl ester, 1,3,5-trihydroxy benzene-2,4,6-trisulphonic acid,and carboxymethyloxysuccinic acid, the various alkali metal, ammoniumand substituted ammonium salts of polyacetic acids such asethylenediamine tetraacetic acid and nitrilotriacetic acid, as well aspolycarboxylates such as mellitic acid, succinic acid, oxydisuccinicacid, polymaleic acid, benzene 1,3,5-tricarboxylic acid,carboxymethyloxysuccinic acid, and soluble salts thereof.

Citrate builders, e.g., citric acid and soluble salts thereof(particularly sodium salt), are polycarboxylate builders of particularimportance for heavy-duty liquid detergent formulations due to theiravailability from renewable resources and their biodegradability.Citrates can also be used in granular compositions, especially incombination with zeolite and/or layered silicate builders.Oxydisuccinates are also especially useful in such compositions andcombinations.

Other suitable builders are disclosed in U.S. Pat. No. 4,566,984, Bush,issued Jan. 28, 1986; U.S. Pat. No. 4,144,226, Crutchfield et al.,issued Mar. 13, 1979 and in U.S. Pat. No. 3,308,067, Diehl, issued Mar.7, 1967 and U.S. Pat. No. 3,723,322.

Fatty acids, e.g., C₁₂-C₁₈ monocarboxylic acids, can also beincorporated into the cleaning compositions alone, or in combinationwith the aforesaid builders. In embodiments wherein phosphorus-basedbuilders are used the various alkali metal phosphates, inter alia,sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphatecan be used. Phosphonate builders such asethane-1-hydroxy-1,1-diphosphonate and other known phosphonates asdescribed in U.S. Pat. Nos. 3,159,581; 3,213,030; 3,422,021; 3,400,148and 3,422,137.

Dispersants

The cleaning compositions of the present invention may comprise fromabout 0.01% to about 10% by weight of the cleaning composition of one ormore polyalkyleneimine dispersants as described in U.S. Pat. No.4,597,898 Vander Meer, issued Jul. 1, 1986; European Patent Application111,965 Oh and Gosselink, published Jun. 27, 1984; European PatentApplication 111,984 Gosselink, published Jun. 27, 1984; European PatentApplication 112,592 Gosselink, published Jul. 4, 1984; U.S. Pat. No.4,548,744 Connor, issued Oct. 22, 1985; and U.S. Pat. No. 5,565,145Watson et al., issued Oct. 15, 1996. However, any suitable clay/soildispersant or anti-redepostion agent can be used in the cleaningcompositions of the present invention.

The cleaning compositions of the present invention may comprise fromabout 0.01% to about 10% by weight of the cleaning composition of one ormore polymeric polycarboxylates and polyethylene glycols. For example,polymeric polycarboxylates and polyethylene glycols derived from acrylicacid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid,aconitic acid, mesaconic acid, citraconic acid and methylenemalonicacid. These monomers can be used alone, in combination with each othermonomers or in combination of units such as vinylmethyl ester, styrene,ethylene, and the like, provided that such segments do not constitutemore than about 40% by weight of said polymer.

One embodiment of the present invention comprises from about 0.01% toabout 10% by weight of the cleaning composition of polymericpolycarboxylates derived from acrylic acid having an average weightmolecular weight of from about 2,000 to about 10,000. In anotherembodiment of the present invention, the cleaning composition comprisespolymeric polycarboxylates derived from acrylic acid having an averageweight molecular weight of from about 4,000 to about 7,000 or from about4,000 to about 5,000. Polyacrylates of this type are disclosed in U.S.Pat. No. 3,308,067 Diehl, issued Mar. 7, 1967.

In addition, acrylic/maleic-based copolymers having average weightmolecular weights ranging from about 2,000 to about 100,000 are usefulin the present invention. However, depending upon the embodiment,molecular weight ranges may include from about 5,000 to about 75,000,and from about 7,000, to about 65,000. The ratio of acrylate to maleatesegments in such copolymers will generally range from about 30:1 toabout 1:1, however, about 10:1 to about 2:1 is also useful as a furtherembodiment. Acrylate/maleate copolymers described in European PatentApplication No. 66915, published Dec. 15, 1982, and EP 193,360,published Sep. 3, 1986.

A further embodiment of the present invention comprises from about 0.01%to about 10% by weight of the cleaning composition of polyethyleneglycol (PEG) having an average weight molecular weight range of fromabout 500 to about 100,000; preferably from about 1,000 to about 50,000;and more preferably from about 1,500 to about 10,000.

Enzymes

The cleaning composition can comprise one or more detergent enzymeswhich provide cleaning performance and/or fabric care benefits. Examplesof suitable enzymes include, but are not limited to, hemicellulases,peroxidases, proteases, cellulases, xylanases, lipases, phospholipases,esterases, cutinases, pectinases, keratanases, reductases, oxidases,phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases,pentosanases, malanases, β-glucanases, arabinosidases, hyaluronidase,chondroitinase, laccase, and known amylases, or mixtures thereof. Apreferred combination is a cleaning composition having a cocktail ofconventional applicable enzymes like protease, lipase, cutinase and/orcellulase in conjunction with the amylase of the present invention.

Enzyme Stabilizers

Enzymes for use in cleaning composition can be stabilized by varioustechniques. The enzymes employed herein can be stabilized by thepresence of water-soluble sources of calcium and/or magnesium ions inthe finished compositions that provide such ions to the enzymes.

Chelating Agents

The cleaning compositions herein may also optionally contain one or moreiron and/or manganese chelating agents. Such chelating agents can beselected from the group consisting of amino carboxylates, aminophosphonates, polyfunctionally-substituted aromatic chelating agents andmixtures therein, all as hereinafter defined. Amino carboxylates usefulas optional chelating agents include ethylenediaminetetracetates,N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates,ethylenediamine tetraproprionates, triethylenetetraaminehexacetates,diethylenetriaminepentaacetates, and ethanoldiglycines, alkali metal,ammonium, and substituted ammonium salts therein and mixtures therein.Amino phosphonates are also suitable for use as chelating agents in thecompositions of the invention when at lease low levels of totalphosphorus are permitted in detergent compositions, and includeethylenediaminetetrakis (methylenephosphonates) as DEQUEST®. Preferred,these amino phosphonates to not contain alkyl or alkenyl groups withmore than about 6 carbon atoms. Polyfunctionally-substituted aromaticchelating agents are also useful in the compositions herein. See U.S.Pat. No. 3,812,044, issued May 21, 1974, to Connor et al. Preferredcompounds of this type in acid form are dihydroxydisulfobenzenes such as1,2-dihydroxy-3,5-disulfobenzene. A preferred biodegradable chelator foruse herein is ethylenediamine disuccinate (“EDDS”), especially the [S,S]isomer as described in U.S. Pat. No. 4,704,233, Nov. 3, 1987, to Hartmanand Perkins. If utilized, these chelating agents will generally comprisefrom about 0.1% to about 10% by weight of the cleaning composition sherein. More preferably, if utilized, the chelating agents will comprisefrom about 0.1% to about 3.0% by weight of such compositions.

Brightener

Any optical brighteners or other brightening or whitening agents knownin the art can be incorporated at levels typically from about 0.01% toabout 1.2%, by weight, into the cleaning compositions herein. Commercialoptical brighteners which may be useful in the present invention can beclassified into subgroups, which include, but are not necessarilylimited to, derivatives of stilbene, pyrazoline, coumarin, carboxylicacid, methinecyanines, dibenzothiophene-5,5-dioxide, azoles, 5- and6-membered-ring heterocycles, and other miscellaneous agents. Specificexamples of optical brighteners that are useful in the presentcompositions are those identified in U.S. Pat. No. 4,790,856, issued toWixon on Dec. 13, 1988. See also U.S. Pat. No. 3,646,015, issued Feb.29, 1972 to Hamilton.

Phase Stabilizers

The cleaning composition according to the present invention mayoptionally comprise one or more phase stabilizers. If utilized, phasestabilizers will generally comprise from about 0.01% to about 50% byweight of the cleaning composition. Suitable phase stabilizers for usein the present invention include, but are not limited to solvents suchas ethanol, 1,2 propanediol and monoethanol amine.

Soil Release Agents

The cleaning compositions according to the present invention mayoptionally comprise one or more soil release agents. If utilized, soilrelease agents will generally comprise from about 0.01% to about 10% byweight of the cleaning composition.

Soil release agents suitable for use in the present invention aredescribed in U.S. Pat. No. 5,843,878 Gosselink et al., issued Dec. 1,1998; U.S. Pat. No. 5,834,412 Rohrbaugh et al., issued Nov. 10, 1998;U.S. Pat. No. 5,728,671 Rohrbaugh et al., issued Mar. 17, 1998; U.S.Pat. No. 5,691,298 Gosselink et al., issued Nov. 25, 1997; U.S. Pat. No.5,599,782 Pan et al., issued Feb. 4, 1997; U.S. Pat. No. 5,415,807Gosselink et al., issued May 16, 1995; U.S. Pat. No. 5,182,043 Morrallet al., issued Jan. 26, 1993; U.S. Pat. No. 4,956,447 Gosselink et al.,issued Sep. 11, 1990; U.S. Pat. No. 4,976,879 Maldonado et al. issuedDec. 11, 1990; U.S. Pat. No. 4,968,451 Scheibel et al., issued Nov. 6,1990; U.S. Pat. No. 4,925,577 Borcher, Sr. et al., issued May 15, 1990;U.S. Pat. No. 4,861,512 Gosselink, issued Aug. 29, 1989; U.S. Pat. No.4,877,896 Maldonado et al., issued Oct. 31, 1989; U.S. Pat. No.4,702,857 Gosselink et al., issued Oct. 27, 1987; U.S. Pat. No.4,711,730 Gosselink et al., issued Dec. 8, 1987; U.S. Pat. No. 4,721,580Gosselink issued Jan. 26, 1988; U.S. Pat. No. 4,000,093 Nicol et al.,issued Dec. 28, 1976; U.S. Pat. No. 3,959,230 Hayes, issued May 25,1976; U.S. Pat. No. 3,893,929 Basadur, issued Jul. 8, 1975; and EuropeanPatent Application 0 219 048, published Apr. 22, 1987 by Kud et al.

Further suitable soil release agents are described in U.S. Pat. No.4,201,824 Voilland et al.; U.S. Pat. No. 4,240,918 Lagasse et al.; U.S.Pat. No. 4,525,524 Tung et al.; U.S. Pat. No. 4,579,681 Ruppert et al.;U.S. Pat. No. 4,220,918; U.S. Pat. No. 4,787,989; EP 279,134 A, 1988 toRhone-Poulenc Chemie; EP 457,205 A to BASF (1991); and DE 2,335,044 toUnilever N.V., 1974.

PREPARATIVE EXAMPLES Example 1 Synthesis of C₁₆-C₁₈ ACAE from MPEG 6.5being Substantially Free of R₁E₁ and R₁E₂

In a dried 1-liter 3 neck round bottom flask fitted with a gas inlet,mechanical stirrer, and a y-tube fitted with a thermometer and a gasoutlet, triethylene glycol monomethyl ether (126 g, 0.77 moles) andsodium (1.01 g, 0.044 moles) is heated under a nitrogen atmosphere to120° C. with stirring to form the alkoxide. Ethylene oxide (119 g, 2.70moles) is introduced as a gas at rate of 0.70 g/minute to give thepoly(ethylene glycol)monomethyl ether with an average ethoxylation of6.5. To this is added C₁₆₋₁₈ fatty acid methyl ester (240 g, 0.85 moles)and sodium methoxide (2.51 g, 0.046 moles) then heated to 100° C. whilereducing the pressure to about 0.267 kPa (2 mm Hg) over a period of 5hours in Kugelrohr (bulb to bulb) distillation apparatus. The reactionis completed and excess starting C₁₆₋₁₈ fatty acid methyl ester isremoved by increasing temperature and vacuum to 180° C. and about 0.033kPa (0.25 mm Hg). The cooled reaction mixture is diluted with 500 ml ofanhydrous diethyl ether, filtered and stirred over AMBERLYST 15®.Resultant suspension is filtered through CELITE® and the ether isremoved using a roto-vap under reduced pressure via water aspirator togive an ACAE with the resultant ethoxylate distribution as depicted inFIG. 2.

Example 2 Ethoxylation of Triethylene Glycol Monomethyl Ether

In a dried 1-liter 3 neck round bottom flask fitted with a gas inlet,mechanical stirrer, and a y-tube fitted with a thermometer and a gasoutlet, triethylene glycol monomethyl ether (202 g, 1.23 moles) andsodium (1.56 g, 0.068 moles) is heated under a nitrogen atmosphere to120° C. with stirring to form the alkoxide. ethylene oxide (298 g, 6.77moles) is introduced as a gas at rate of 0.70 g/minute. Mixture isneutralized with concentrated HCl after diluting with 500 mL ofmethanol. Methanol is removed using a roto-vap under reduced pressurevia water aspirator. Resultant cloudy yellow oil is dissolved in 500 mLanhydrous ether and dried over 20 g of sodium sulfate, filtered throughCelite and the ether is removed using a roto-vap under reduced pressurevia water aspirator to give the poly(ethylene glycol)monomethyl etherwith an average ethoxylation of 8.5.

Example 3 Synthesis of C₁₆-C₁₈ ACAE from MPEG 8.5 being SubstantiallyFree of R₁E₁ and R₁E₂

In a dried 1-liter round bottom flask C₁₆₋₁₈ fatty acid methyl ester (76g, 0.27 moles), MPEG 8.5 from triethylene glycol monomethyl etheraccording to Example 1 (101 g, 0.25 moles) and sodium methoxide (1.1 g,0.02 moles) is heated to 100° C. while reducing the pressure to about0.267 kPa (2 mm Hg) over a period of 5 hours in Kugelrohr (bulb to bulb)distillation apparatus. The reaction is completed and excess startingC₁₆₋₁₈ fatty acid methyl ester is removed by increasing temperature andvacuum to 180° C. and about 0.033 kPa (0.25 mm Hg). The cooled reactionmixture is diluted with 250 ml of anhydrous diethyl ether, filtered andstirred over AMBERLYST 15®. Resultant suspension is filtered throughCELITE® and the ether is removed using a roto-vap under reduced pressurevia water aspirator to give an ACAE with the formula (I):

(I) wherein R₁ is methyl, R₂ is C₁₆-C₁₈ and x is 8.5.

Example 4 Synthesis of C₁₆-C₁₈ ACAE from MPEG 7.2 R₁E₁ and R₁E₂ PostSynthesis Removal

In a dried 1-liter round bottom flask C₁₆₋₁₈ fatty acid methyl ester (78g, 0.28 moles), MPEG 7.2 (88 g, 0.25 moles) and sodium methoxide (1.1 g,0.02 moles) is heated to 100° C. while reducing the pressure to about2.67 kPa (2 mm Hg) over a period of 5 hours in Kugelrohr (bulb to bulb)distillation apparatus. Reaction is completed, excess starting C₁₆₋₁₈fatty acid methyl ester and R₁E₁ and R₁E₂ are removed by increasingtemperature and vacuum to 180° C. and about 0.033 kPa (0.25 mm Hg) thenfurther increasing temperature to 210° C. and about 6.67 Pa (0.05 mmHg). The cooled reaction mixture is diluted with 250 ml of anhydrousdiethyl ether, filtered and stirred over AMBERLYST 15®. The resultantsuspension is filtered through CELITE® and the ether is removed using aroto-vap under reduced pressure via water aspirator to give an ACAE withthe formula (I):

(I) wherein R₁ is methyl, R₂ is C₁₆-C₁₈ and x is 7.2.

Example 5 Synthesis C₁₆-C₁₈ACAE from Stripped MPEG 7.2

In a dried 1-liter round bottom flask MPEG 7.2 (88 g, 0.25 moles) isheated to 100° C. at a reduced pressure to about 2.67 kPa (2 mm Hg) toremove ethylene glycol alkyl ether (R₁O(CH₂CH₂O)H) and diethylene glycolalkyl ether (R₁O(CH₂CH₂O)₂H). To this stripped MPEG is added C₁₆₋₁₈fatty acid methyl ester (78 g, 0.28 moles) and sodium methoxide (1.1 g,0.02 moles) then heated to 100° C. while reducing the pressure to about2.67 kPa (2 mm Hg) over a period of 5 hours in Kugelrohr (bulb to bulb)distillation apparatus. Reaction is completed and excess starting C₁₋₁₈fatty acid methyl ester is removed by increasing temperature and vacuumto 180° C. and about 0.033 kPa (0.25 mm Hg). The cooled reaction mixtureis diluted with 250 ml of anhydrous diethyl ether, filtered and stirredover AMBERLYST 15®. The resultant suspension is filtered through CELITE®and the ether is removed using a roto-vap under reduced pressure viawater aspirator to give an ACAE with the formula (I):

(I) wherein R₁ is methyl, R₂ is C₁₆-C₁₈ and x is 7.2.

Example 6 Synthesis of C₁₆-C₁₈ ACAE from Polyethylene Glycol MonobutylEther 10.5 Containing Substantially No R₁E₁-R₁E₂

In a dried 1-liter round bottom flask C₁₆₋₁₈ fatty acid methyl ester (61g, 0.22 mols), BPEG 10.5, free of ethylene glycol butyl ether anddiethylene glycol butyl ether, (94 g, 0.17 mols) and sodium methoxide(0.94 g, 0.017 mols) is heated to 100° C. while reducing the pressure toabout 2.67 kPa (2 mm Hg) over a period of 5 hours in Kugelrohr (bulb tobulb) distillation apparatus. Reaction is completed and excess startingC₁₆₋₁₈ fatty acid methyl ester is removed by increasing temperature andvacuum to 180° C. and about 0.033 kPa (0.25 mm Hg). The cooled reactionmixture is diluted with 250 ml of anhydrous diethyl ether, filtered andstirred over AMBERLYST 15®. The ensuing suspension is filtered throughCELITE® and the ether is removed using a roto-vap under reduced pressurevia water aspirator to give the ethoxylated methyl ester.

1. A cleaning composition comprising: a) from about 0.01% to about 30%by weight of said composition of one or more product of any of claims 1,2, or 7, b) from about 1% to 60% of said composition of a surfactantsystem, said surfactant system comprising: i) from 0.01% by weight ofthe surfactant system of one or more anionic surfactants, said anionicsurfactants selected from the group consisting of linear alkyl benzenesulphonates, modified alkyl benzene sulphonates; linear alkyl sulfates,mid-chain branched sulfates, linear alkyleneoxy sulfates, mid-chainbranched alkyleneoxy sulfates; and mixtures thereof; ii) optionally,from 0.01% of said surfactant system of one or more nonionic surfactantsselected from the group consisting of alcohols, alcohol ethoxylates,polyoxyalkylene alkylamides, and mixtures thereof; and c) the balance ofsaid composition comprising carriers and other adjunct ingredients.